US3749749A - Production of 2,2-dialkyl-3-acyloxypropanals - Google Patents

Production of 2,2-dialkyl-3-acyloxypropanals Download PDF

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US3749749A
US3749749A US00104121A US3749749DA US3749749A US 3749749 A US3749749 A US 3749749A US 00104121 A US00104121 A US 00104121A US 3749749D A US3749749D A US 3749749DA US 3749749 A US3749749 A US 3749749A
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parts
acid
formaldehyde
isobutyraldehyde
reaction
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F Merger
W Fuchs
T Dockner
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • the invention relates to a process for the production of 2,2-dialkyl-3-acyloxypropanals by acyloxymethylation of secondary aldehydes with carboxylic acids and formaldehyde in the presence of strong acids with simultaneous removal of water from the reaction mixture.
  • acetoxypivalaldehyde can be prepared by esterification of 2,2-dimethyl-3-hydroxypropanal with acetic acid (US. Pat. 3,251,876).
  • the synthesis of 2,2- dialkyl-3-alkanoyloxypropanals from monobasic carboxylic acids, formaldehyde and dialkylacetaldehydes by heating in the presence of mineral acids at from 50 to 120 C. is described in US. Pat. 3,374,267.
  • An article in Annalen der Chemie 627 (1959), 96 to 106 describes the condensation of isobutyraldehyde, formaldehyde and acetic acid.
  • the said methods give mixtures of acyloxypivalaldehyde, hydroxypivalaldehyde and often a considerable proportion of higher condensation products of hydroxypivaldehyde alone or of its adduct with for example acetoxypivalaldehyde.
  • the yields of fl-acyloxyaldehydes are consequently low.
  • it is difficult to isolate the fl-acyloxyaldehydes because they differ only slightly in their boiling points from the ,B-hydroxyaldehydes.
  • the presence of fi-hydroxyaldehydes makes further processing, for example in oxidation with oxygen to form ,B-acyloxycarboxylic acids (US. Pat. 3,251,876) more difficult.
  • R and R may be identical or different and each denotes an aliphatic radical, R may also denote hydrogen or a cycloaliphatic, araliphatic or aromatic radical and/ or R and R together with the adjacent carbon atom may be members of a cycloaliphatic ring, are obtained advantageously by reaction of a carboxylic acid with formaldehyde and a secondary aliphatic aldehyde in the presence of a strong acid when a carboxylic acid having the general formula:
  • the process according to the invention gives 2,2-dialkyl-3-acyloxypropanals by a simpler and more economical method, in better yields and purity and without substantial resin formation. It is surprising that the reaction can be carried out at all in an anhydrous medium in solvents which have little suitability for ion reactions and that it proceeds at an increased speed and with higher selectivity.
  • Aromatic carboxylic acids may also be used as starting material (II). Separation of the end product from the reaction mixture may be carried out in a simpler Way without expensive fractional distillations and with less wastage of unreacted starting material (II) than in the case of US. Pat. 3,374,267.
  • Starting material (Il) may be reacted with formaldehyde and with starting material (III) in the stoichiometric amount or in excess, preferably in a molar excess of starting material (II) to starting material (III) of from 1.2:1 to 5:1 and of formaldehyde to starting material (III) of from 1:1 to 1:1.5.
  • Preferred starting materials (II) and (III) and consequently preferred end products (I) are those in whose formulae R R and R may be different or identical and each denotes alkyl having one to eight carbon atoms, R may also denote hydrogen, cycloalkyl having five to ten carbon atoms, aralkyl having seven to twelve carbon atoms, phenyl, naphthyl and/or R and R together with the adjacent carbon atom may denote members of a five-membered to eight-membered cycloalkyl ring.
  • the said radicals and rings may bear, as substituents, groups and/ or atoms which are inert under reaction conditions, for example chlorine or bromine atoms, nitro or cyano groups, alkyl or alkoxy groups having one to four carbon atoms.
  • the alkyl radicals may be linear or branched.
  • starting materials (II) which may be used: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hexanoic acid, 2-ethylhexanoic acid, cyclohexyloic acid, cyclooctyloic acid, cyclododecyloic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, a,a-dichlorobutyric acid, 06- chloroisobutyric acid, a-bromoisobutyric acid, bromoacetic acid, iodoacetic acid, benzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 3,4-dichlorobenzoic acid, p-methoxybenzoic acid, fi-naphthyloic acid, phenylacetic acid, a,a-dichloropropi
  • starting materials (III) isobutyraldehyde, Z-methylbutanal, Z-methylpentanal, 2- ethylhexanal, cyclohexylaldehyde and cyclooctylaldehyde.
  • Formaldehyde may be used in anhydrous form as paraformaldehyde or as trioxane. It is a considerable advantage of the process according to the invention that it is possible to use cheap aqueous formaldehyde solutions. The proportion of water in the formalin solution is surprisingly separated from the reaction mixture without appreciable loss of formaldehyde and without the said beneficial results being affected.
  • the catalysts in the reaction may be strong acids, as a rule those having a dissociation constant of less than for example trichloroacetic acid, phosphoric acid, cyanoacetic acid, o-brornobenzoic acid, p-chlorobenzoic acid.
  • Arylsulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, sulfuric acid and phosphoric acid are preferred.
  • the starting material (11) is itself a strong acid, it may also serve at the same time as the catalyst for the reaction.
  • the catalyst is conveniently used in an amount of from 0.1 to 2.5% molar with reference to starting material (II).
  • the reaction is generally carried out at a temperature of from 40 to 150 C., preferably at from 60 to 90 C., at atmospheric or superatmospheric pressure, continuously or batchwise. It is convenient to use solvents which form azeotropes with water which boil Within the said temperature range at atmospheric pressure, subatmospheric pressure or superatmospheric pressure.
  • solvents examples include benzene, toluene, xylene, diisobutylene, hexane, chloroform, carbon tetrachloride. They are used in variable amounts according to the solubility of the components, as a rule in an amount of from 100 to 200% by volume based on starting material III). Solubilizers such as dioxane and tetrahydrofuran may be used if the starting materials are only sparingly soluble. The said solvents are suitable whether the starting materials are anhydrous or contain water.
  • the reaction may be carried out as follows: A mixture of the starting materials with the catalyst with or without a solvent and solubilizer is kept for from half an hour to twelve hours, as a rule for from one hour to six hours, at the reaction temperature. Water formed is removed during the reaction, preferably by azeotropic distillation together with the solvent. The water may be removed in portions or advantageously continuously. Not only is the water formed removed, but also any water present at the beginning of the reaction, for example water serving as solvent for formaldehyde or water introduced in admixture with acetic acid. The end product is removed from the reaction mixture after the reaction by a conventional method, for example by distillation. The amounts of solvent and unreacted starting material (II) may be used again.
  • EXAMPLE 1 In a stirred vessel fitted with a water separator, 60 parts of paraformaldehyde, 500 parts of acetic acid and 300 parts by volume of benzene are boiled while stirring.
  • COMPARATIVE EXAMPLE 1 a 60 parts of paraformaldehyde, 1240 parts by volume of acetic acid, 144 parts of isobutyraldehyde and 15 parts of sulfuric acid are heated for six hours at 70 C. without removing water, cooled and poured into 1300 parts by volume of water. The organic phase and the extracts of the aqueous phase with ether are united, washed with 200 parts by volume of a saturated common salt solution and dried with anhydrous sodium sulfate. Fractionation of the organic solution at 15 mm. gives 153 parts (about 53% of theory) of a mixture of acetoxypivalaldehyde and hydroxypivalaldehyde (molar ratio of about 9:1) having a boiling point of from 76 to 84 C.
  • EXAMPLE 2 800 parts of acetic acid, 300 parts by volume of benzene, 200 parts of a 37% by Weight aqueous formaldehyde solution, 144 parts of isobutyraldehyde and 5 parts of p-toluenesulfonic acid are boiled in a stirred vessel fitted with a water separator until completion of water separation. The mixture is worked up analogously to Example 1, 262 parts (91% of theory based on isobutyraldehyde) of acetoxypivalaldehyde is obtained at from 70 to 72 C. and 12 mm.
  • EXAMPLE 3 While stirring, 700 parts of 99.5% formic acid, 300 parts by volume of benzene, 60 parts of paraformaldehyde, 144 parts of isobutyraldehyde and 4 parts of ptoluenesulfonic acid are boiled in a stirred vessel fitted with a water separator until completion of water separation (about four hours). The mixture is fractionated through a column filled with glass packing. 250 parts (96% of theory based on isobutyraldehyde and formaldehyde) of formyloxypivalaldehyde is obtained having a boiling point of 74 C. at 18 mm.
  • EXAMPLE 4 As described in Example 3, 486 parts of trichloroacetic acid, 30 parts of paraformaldehyde and 72 parts of isobutyraldehyde in parts by volume of benzene are boiled until completion of water separation (two to three hours). The mixture is distilled. 151 parts (61.4% of theory based on formaldehyde and isobutyraldehyde) of trichloroacetoxypivalaldehyde is obtained as a colorless liquid having a boiling point of 129 C. at 15 mm.
  • EXAMPLE 5 As described in Example 3, 282 parts of chloroacetic acid, 30 parts of paraformaldehyde and 72 parts of isobutyraldehyde, 150 parts of benzene and 2 parts of ptoluenesulfonic acid are boiled until the separation of water is ended (three to four hours). The mixture is distilled through a column filled with glass packing. 133 parts (74.6% of theory with reference to formaldehyde and isobutyraldehyde) of chloroacetoxypivalaldehyde is obtained having a boiling point of from 118 to 120 C. at '13 mm.
  • EXAMPLE 6 As described in Example 5, 384 parts of dichloroacetic acid, 30 parts of paraformaldehyde and 144 parts of isobutyraldehyde are condensed in the presence of 3 parts of p-toluenesulfonic acid. The mixture is distilled.
  • EXAMPLE 7 As in Example 5, 426 parts of u,a-dichloropropionic acid, 30 parts of paraformaldehyde and 72 parts of isobutyraldehyde are condensed for about four hours in the presence of 3 parts of p-toluenesulfonic acid. The mixture is distilled. 141 parts (62.4% of theory with reference to formaldehyde and isobutyraldehyde) of a,a-dichloropropionyloxypivalaldehyde is obtained having a boiling point of 76 C. at 0.3 mm.
  • EXAMPLE 8 As described in Example 5, 530 parts of isobutyric acid, 30 parts of paraformaldehyde and 72 parts of isobutyraldehyde are condensed in the presence of 5 parts of ptoluenesulfonic acid. 127.5 parts (74% of theory based on formaldehyde and isobutyraldehyde) of isobutyryloxypivalaldehyde is obtained having a boiling point of 100 C. at 20 mm.
  • EXAMPLE 9 As described in Example 5, 300 parts of acetic acid, 30 parts of paraformaldehyde and 100 parts of 2-methylpentanal are condensed in the presence of 3 parts of ptoluenesulfonic acid. The mixture is distilled. 153 parts (88.8% of theory with reference to formaldehyde and 2- methylpentanal) of 2-methyl-2-n-propyl-3-acetoxypropanal is obtained having a boiling point of 105 C. at 16 mm.
  • EXAMPLE 10 As described in Example 5, 300 parts of acetic acid, 30 parts of paraformaldehyde and 128 parts of Z-ethylhexanal are condensed in the presence of 3 parts of p-toluenesulfonic acid. The mixture is distilled. 155.5 parts (76.2% of theory with reference to formaldehyde and 2-ethylhexanal) of 2ethyl-2-n-butyl3-acetoxypropanal is obtained having a boiling point of 120 C. at mm.
  • EXAMPLE 11 As described in Example 5, 300 parts of acetic acid, 30 parts of paraformaldehyde and 112 parts of cyclohexylaldehyde are condensed in the presence of 3 parts of ptoluenesulfonic acid. The mixture is distilled. 148 parts (80% of theory based on formaldehyde and cyclohexylaldehyde) of 1 acetoxymethylhexahydrobenzaldehyde is obtained having a boiling point of 99 to 100 C. at '6 mm.
  • EXAMPLE 12 As described in Example 5, 366 parts of benzoic acid, 30 parts of paraformaldehyde and 72 parts of isobutyraldehyde are condensed in 500 parts of benzene in the presence of 10 parts of p-toluenesulfonic acid for twelve hours. The mixture is distilled. 99 parts (51% of theory with reference to formaldehyde and isobutyraldehyde) of benzoyloxypivalaldehyde is obtained having a boiling point of 170 C. at 20 mm.
  • EXAMPLE 13 As described in Example 5, 380 parts of 3,4 dichlorobenzoic acid, 30 parts of paraformaldehyde and 72 parts of isobutyraldehyde are condensed in 500 parts of benzene in the presence of 10 parts of p-toluenesulfonic acid for twelve hours. The mixture is distilled. 110 parts (42% of the theory with reference to paraformaldehyde and isobutyraldehyde) of 3,4-dichlorobenzoyloxypivalaldehyde is obtained having a boiling point of 165 to 167 C. at 1 mm. The melting point is 45 to 46 C. (recrystallized from petroleum ether).
  • R R and R may be identical or different and each may denote an aliphatic radical
  • R may also denote hydrogen, a cycloaliphatic, araliphatic, or aromatic radical and/or R and R together with the adjacent carbon atom, denote members of a cycloaliphatic ring, by reaction of a carboxylic acid with formaldehyde and a secondary aliphatic aldehyde in the presence of a strong acid having a dissociation constant of less than 10- wherein at least a stoichiometric amount of a carboxylic acid having the general formula:
  • reaction is carried out in a molar ratio of starting material (II) to starting material (III) of from 1.2:1 to 5:1 and of formaldehyde to starting material (II) of from 1:1 to 1:15.
  • a process as claimed in claim 1 carried out at a temperature of from 60 to C.
  • reaction is carried out in a molar ratio of starting material (II) to starting material (III) of from 1.2:1 to 5 :1 and of formaldehyde to starting material (II) of from 1:1 to 1:15, the catalyst is used in an amount of from 0.1 to 2.5 molar with reference to starting material (II), the reaction temperature is 40-150 C.
  • R R and R each denotes alkyl having one to eight carbon atoms, R may also denote hydrogen, cycloalkyl having five to ten carbon atoms, aralkyl having seven to twelve carbon atoms, phenyl, or naphthyl or said groups having, as substituents, chlorine, bromine, nitro, cyano, alkyl or alkoxy having 1-4 carbon atoms.
  • starting material (11) is formic acid, acetic acid, propionic acid,
  • a,a-dichloropropionic acid and starting material (III) is isobutyraldchyde, Z-mcthylbutanal, Z-methylpentanal, 2- 10 260-465 D, 465.4, 469, 471 R, 471 A, 473 R, 476 R, ethylhcxanal, cyclohexylaldchyde or cyclooctylaldehyde. 484 R, 487, 494

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US00104121A 1970-01-07 1971-01-05 Production of 2,2-dialkyl-3-acyloxypropanals Expired - Lifetime US3749749A (en)

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DE2000511A DE2000511C3 (de) 1970-01-07 1970-01-07 Verfahren zur Herstellung von 2,2-Dialkyl-3-acyloxy-propanalen

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DE (1) DE2000511C3 (fr)
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GB (1) GB1326717A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400290A (en) * 1981-10-01 1983-08-23 International Flavors & Fragrances Inc. Process for augmenting or enchancing the aroma of detergent compositions using oxyalkyl esters
US4493801A (en) * 1980-12-02 1985-01-15 Basf Aktiengesellschaft Preparation of tertiary alcohols

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4493801A (en) * 1980-12-02 1985-01-15 Basf Aktiengesellschaft Preparation of tertiary alcohols
US4400290A (en) * 1981-10-01 1983-08-23 International Flavors & Fragrances Inc. Process for augmenting or enchancing the aroma of detergent compositions using oxyalkyl esters

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FR2075228A5 (fr) 1971-10-08
DE2000511B2 (de) 1979-01-18
GB1326717A (en) 1973-08-15
BE761159A (fr) 1971-06-30
DE2000511C3 (de) 1979-09-13
DE2000511A1 (de) 1971-07-22

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